Process for breaking petroleum emulsions employing certain polyepoxide treated amine-modified thermoplastic phenol-aldehyde resins



U i d States Pa en P ocjEs's FOR BREAKING PETROLEUM,EMUL SIONS EMPLOYING CERTAIN POLYEPOX'IDE TREATED AMliNE-MODIFIED THERMOPLASTIC PnENoL-ALnEnYnE RESINS Melvin De Groote, University City, and Kwan-Thrg Siren, Br'entwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application February 24, 1953, Serial No. 338,576

20 Claims. (Cl. 252-338) The present invention is a continuation-in-part of our co-pending application, Serial No. 305,079, filed August 18, 1952, now abandoned. I

The present invention is concerned with demulsification which involves the use of certain polyepoxide-tre'ated amine-modified thermoplastic phenol-aldehyde resins for the resolution of petroleum emulsions. More specifically, the invention is concerned with the breaking of emulsion of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including products obtained by the method of first condensing certain phenol-aldehyde resins, hereinafter described in detail, with certain basic hydroxylated polyamines, having at least one secondary amino group and having not more than 32 carbon atoms in any group attached to any amino nitrogen atom, hereinafter described in detail, and formaldehyde, which condensation is followed by reaction of the resin condensate with certain phenolic polyepoxide's, also hereinafter described in detail, and cogenerically associated compounds formed in the preparation of the polyepoxides.

In preparing diepoxides or the low molal polymers one does usually obtain cogeneric materials which may include monoepoxides. However, the cogeric mixture is invariably characterized by the fact that there is on the average, based on the molecular weight, of course, more than one epoxide group per molecule.

A more limited aspect of the invention is represented by the use of the reaction product .of (A) an aminemodified phenol-aldehyde resin condensate as described, and (B) a member of the class consisting of (1) compounds of the following formulanqc cn-om-OO c 0113' \O/ It so happens that the bulk of information concerned with the preparation of compounds having-two oxirane rings appears in the patent literature and for the most part in the recent patent literature. Thus, in the subsequent text, there are numerous references to such patents for purpose of supplying information and also for purpose of brevity. p v

Notwithstanding the fact that subsequent data will be presented in considerable detail, yet the description becomes somewhat involved and certain facts should be kept in'mind. The epoxides, and particularly the diepoxides may haveno connecting bridge between the pilenolic nuclei as in. the case of a diphenyl derivative or may have a variety of connecting-bridges, i. e. divalent link 2,771,438 Patented Nov. 20, 195d ing radicals. Our preference is that either diphenyl compounds be employed or' else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde.

If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i. e., in preference to the polymer or mixture of polymer and monomer. Y

Stated another way we would prefer to use materials of the kind described, for example, in U. S. Patent 2,530,353, dated November 14, 1950. Said patent describes compounds having the general formula v 2 wherein R is an aliphatic hydrocarbon bridge, each n1,

"ice

independently has one of the values 0 and 1, and X is U. S. Patent No. Dated Inventor July 5, 1939 Sebafer. December 13, 1938. Mlkeska et al. September 26, 1939 Do. 5 April 2, 1940 Do. U July 16, 1940 Cohen et a1. June 3, Rosen et a]. June 17, 1941-.. Rosen,

June 9, 1942 Britton et a1. October 12 1943 Winning et al. November 4, 1947 De Groote et al. December 28 1948 Swern et a1. February 15, 1949 Wyler. February 15, 1949. Do. September 27, 1949. -r Dietzler. November 15, 1949 Mikcska et a1. April 4, 1950 Dietzler et 9.1. April 11, 1950 Bock et al May 2, 1950. Bender et a] July 18, 1950. Stevens et a1. July 18, 1950 Do.

. July 18, 1950 Do.

. October 17, 1950 e Dietzler November 14, 1950.. Havens January 22, 1952 Greeulee.

The compounds having two oxirane rings and employed for combination with the reactive amine-modified, phenol-aldehyde resin condensates as herein described are compounds of the following formula and cogenerically associated compounds formed in their preparationz in which R represents a divalent radical selected from by the elimination of valent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical -S-, the divalent radical 1 'with the amine-modified resin.

. v s 3 V V and the'divalent disulfide radical SS--; and R is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which- R, R, and R'" represent a member of the 10 class of hydrogen and hydrocarbon substituents of the aromatoc nucleus, said substituent member having not over 18 carbon atoms; n represents an'integer selected frorn theclass of zero and l, and n represents a whole a number not greater than 3. The above mentioned com- 1 pounds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solvent-soluble. Reference to being thermoplastic characterizes them as being liquids :at ordinary temperature or readily convertible to liquids by merely heating below 20 the point of pyrolysis and thus differentiates them from infusible resins; Reference to being soluble in an organic solvent means any of the usual organic solvents, such as 4 in the epoxide derivative can combine with a sulfonamide resin. The intention in said U. S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin.

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low; molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a'hydroxylated group or secondary amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent,

i. e., the compound having two oxirane rings and ;tri-

ethanolamine. Proceeding with the example previously.

described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

(condensate) alcohols, ketones, esters, ethers, mixed so1vents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infnsible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containingthe epoxy rings before reacting In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexylether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimeth- 40 oxytetraethyleneglycol.

The expression epoxy is not usually limited to the 'l,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as theoxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-

epoxide rings or oxirane rings in the alpha-omega position. Thisis a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplestfiie'poxide which contains at least 4 carbon atomsfandis formally described as l,2-epoxy-3,4-epoxyhutanfetiihz fiA ep y f It well" maybe that even though the previously suggested formula represents the principal component, or

components, of .the resultant or reaction product descr bed lnthe previous text, itmay-be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as com plex resmous epoxides which are polyether derivatives of,

polyhydri'c phenols containing an average of more than in the usual thermosetting resins. Note, for example, that said U. S. Patent No. 2,421,295 describes products where- (condensate) in which the various characters have their previous significance and the characterization condensate is simplyan abbreviation for the condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but-may include-water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc.

be significantly basic and it is immaterial whether aqueous solubility represents an anhydr-o base or the free base (combination with water) or a salt form such as the ace- The purpose in this instance is to dif-' ferentiate from insoluble resinous materials, particularly tate, chloride,'etc.

those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where arr-insoluble material is desired, but also serves to.

emphasize the fact-that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid For instance, the prod-;

ucts freed from any solvent can be shaken with 5 to 20 times their weight of distilled water at ordinary temperature and show at least some tendency towards being selfdispersing. The solvent which is generally tried is xylene. If xyIene alone does not :serve then a mixture of xylene 5 and methanol, for instance, parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture; for instance, 5% to 10% of acetone.

The polyepoxide-treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and, valuable derivatives can be obtained by further reaction with ethylene oxide, propyleneyoxide, ethylene imine,

etc. I

reacted with a product having both a nitrogen group and a l,2,-epoxy group, such as 3 dialkylaminoepoxypropane."

See U. '8. Patent No. 2,520, 093, dated August 22, 1950, to Groll.

.We particularly prefer to use those products which as, such-.or' in the form-0f the free base or hydrate, i. e., com}. bination withwater'or particularly in the form of a lowmolal organicacid salt such'as the gluconates or the acetate. or hydroxy acetate, have sufliciently hydrophile, charactertoatleastjmeet the test set forth in U; S. Patent In other words, the nitrogengroups present, whethertwo or'more, may or may not.

7 Similarly, the polyepoxide-derived compounds can be No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water insoluble solvent, generally xylene, is described as an index of surface activity. I

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble a lthough they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into eight parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the prepara tion of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 5 is concerned with appropriate basic hydroxylated polyamines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compound which are then subjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than "a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are pertectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquid or low-melting solids. Indeed, they tend to form thermosetting resin-s or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as 'free as possible from any monoepoxides and as free as a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably in variably are present, other low molal polymers in coinparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monorners with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory Briefly, then, our

preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It hasbeen pointed out previously that the henolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and. also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This com pound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is Reference has just been made to bis-phenol A anda suitable epoxide derived thereform. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4

isomers predominating and with lesser quantities of the: It is immaterial 2,2 and 4,2 isomers being present. which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be' immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere" substitution of one compound for .the other would'be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies. with equal force and efiect to the other" classes'of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfur-containg;

ing compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic,

even though in comparatively small concentration.

V PART 2v V .The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example, the use; of epichlorohydrin or glycerol dichlorohydrin. If

- a product such: as bis-phenol A is employed the ultimate compound in monomeric form employed as a reactant in the present invention has the following structure:

Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced'which can be indicated by the following struc- 7 Treatment with alkali, of course, forms the epoxy ring.

A number of problems are involved in attempting to produce this compound free from cogeneriematerials of related composition. The difliculty stems from a number of sources and a few of the more important ones'are as follows: a

' (1) The closing of the epoxy ring involves the use of caustic soda or the like which, in turn, is an effective catalyst in causing the ring to open in an oxyalkylation reaction.

Actually, what may happen for any one of a number, of reasons is that one obtains a product in which there is only one epoxide ring and there may, as a matter of fact, be more than one hydroxyl radical as illustrated by the following compounds:

(2) Even if one starts with the reactants in the preferred at times apparently .does, take place in connection with (ilHa OH u Needlessto say, compounds can be formed which cor--' next formula 'is in essence one which, perhaps in an idealized way, establishes the composition of'resinous products availableunder the name of Epon Resins as now sold in the open market. See, also, chemical pamphlet compounds having one,. or in. the present instance, two. substituted foxirane rings, i. e.', substituted 1,2 epoxy. 7

rings. T bus, in manyways it is easier to produce a poly-' mer, particularly a mixture of the monomer, dimer and;

trimer, than it is to produce the monomer alonel (4) As has been pointed out previously, monoepoxides may help resent and, indeed, are almost invariably and inevitably present when one attempts to produce 'poly epoxides,1and particularly diepoxides. The reason is the: one which has been indicated previously, together'with the fact that in the ordinary course of reaction a di-' ep oxide, such as may react with a mole of bis-phenol A to give a mono-' epoxy structure. Indeed, in the subsequent text immedi I ately'following reference ismade to' the dimers, trimersi and tetramers in which two epoxide groups are present.

respond-in every respect except that one terminal epoxide group is absent and in its place is a group having-one chlorine atom and one hydroxylgroup, or else two. hydroxyl :groups, or an unreacted phenolic ring.

(5) Somieirefer'ence has .been made to the presence of a chlorine atom and although v all efiort is directed towards the elimination of any chlorine-containingmolecule yetit is apparent. that this is often an ideal approach rather thana practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and a chlorine atom present. See U. S. Patent No. 2,581,464,.

dated January 8, 1952, to Zech.

e What has been said in regard to the theoretical aspect is, of course, closely related to-the actual method of preparation which is discussed in greater detail in Part 3, particularlysubdivisions A and B; There can be, no clear line between the theoretical aspect andactual preparative steps. However, in order to summarize or illustrate what has been said in Part 1, immediately precedingv reference will be made to a typical example which al-' ready has been employed for purpose of illustration. The particular example is It is obvious that two moles of such material combinereadily with one mole of bis-phenol A,

to produce the product whichis one step further along, at least, towards polymerization.

priorexarnple shows the reaction product obtainedfromi one mole of the bisphenol A and two moles of epichloro-;

hydrin. This product in turn .would represent three moles of bisphenol A and four moles of epichlorohydrin.

For; purpose of brevity, without going any further, the

entitled .Epon Surface-Coating Resins, Shell Chemical Corporation, New York City. The word Epon is a registered trademark of the Shell Chemical Corporation.

In other words, .one.

For the purpose of the instant invention, n may repre- At the expense of repetition of what appeared previe sent a number including zero, and at the most a low ously, it may be well to recall that these materialsmay number such as 1, 2 or 3. This limitation does not vary from simple soluble non-resinous to complex nonexist in actual efforts to obtain resins as differentiated soluble resinous epoxides which are polyether derivatives from the herein described soluble materials' It is quite 5 of polyhydric phenols containing an average of more probable that in the resinous products as marketed for than one epoxide group per molecule and free from'funccoating use the value of n is usually substantially higher. tional groups other than epoxide and hydroxyl groups. Note again what has been said previously that any for- The former are here included, but the latter, i. e., highly mula is, at best, an over-simplification, or at the most resinous or insoluble types, are not. represents perhaps only the more'irnportant or principal I In summary then in light of what hasbeen said, comconstituent or constituents. These materials may vary pounds suitable for reaction with amines may be sumfrom simple non-resinous to complex resinous epoxides marized by the following formula:

which are polyether derivatives of polyhydric phenols or for greater simplicity the formula could be restated containing an average of more than one epoxide group thus:

per molecule and free from functional groups other than in which the various characters have their prior signifiepoxide and hydroxyl groups. 1 3 canoe and in which R is the divalent radical obtained Referring now to what has been said previously, to wit, by the elimination of a hydroxyl hydrogen atom and a. compounds having both an epoxy ring or the equivalent nuclear hydrogen atom from the phenol and also a hydroxyl group, one need go no further than to consider the reaction product of e @OH OH: H H H I H H H I C 7 5H3 I and bisphenol A 1n a mole-for-mole ratio, s1nce the i whi h R, R, and R represent a member of the initial reactant would Yield a Product having an ullfeclass consisting of hydrogen and hydrocarbon substituacted P Y g and two reactive Y Y ladicalsents of the aromatic nucleus, said substituent member Referring again to a previous formula, Consider all having not over 18 carbon atoms; n represents an integer ample Where two moles of blsphenfll A have selected from the class of zero and 1, and n represents acted with 3 moles of epichlorohydrin. The simplest coma whole number not greater than 3. pound formed would be thus:

I z 0H: 7 CH: i z 03 /OH I 0 J 0 CH Such a compound iscomparable to other compounds hav- PART 3 ing both the hydroxyl and epoxy ring such as 9,10-epoxy Sub division A octadecanol. The ease with which this type of compound p-olymerizes is pointed out by U. S. Patent No.

2,457,329, dated December 28, 1948, to Swern et al.

The same difiicu-lty which involves the tendency to The preparations of the diepoxy derivatives of the phenols, which are sometimes referred to as diglycidyl ethers, have been described in a number of patents. For convenience, reference will be made to two only, to wit,

P01Ymerize the Part wmpomds having a reactive aforementioned U. s. Patent 2,506,486, and aforemenring and a hydroxyl radical may be illustrated by comtioned Patent 530 353 Rounds l instead of the oxlfafle n (L P XY Purely by way of illustration, the following diepoxides, flllg) there 15 present a P Y Such lnd or diglycidyl ethers as they are sometimes termed, are

are derivatives of trimethylene oxide rather than ethylene i l d d f r ur of illustration. These particular oxide. See U. S. Patents Nos. 2,462,047 and 2,462,048, compounds are. described in the two patents just men-' both dated February 15, 1949, to Wyler. tioned.

, g,771,4es 11 12 TABLE! I'I'IEXV- f Patent ample Diphenol Diglycldyl ether referenee CH1(C H4OH), Di(eporypropo ryphenyl)methane 2, 506, 486 OH;CH(C9H4OH)1-- Di(epoxypropoxyphenyl)methyhnethane 2, 506. 486 I (OH3)1C(CflH40H)2 D1(epoxypropoxyphenybdimethylmethane 2, 506, 486 O1H|C (0H (O l-140mg. Di(epoxypropoxyphenyl)ethylmethylmethan 2, 506, 486 (011E920 (00H40H)2. Di(epoxypropoxypheny1)d1ethy1methane 2, 506, 486 CHaC CaHh) (O HxOH) 2. Di(epoirypropoxyphenyl)methylpropylmetha 2, 506, 486 -CH5O CuHs) (C5H4OH);. Di(epoxypropoxyphenyl) 2, 506. 486 ;-C1HuO(CH )(O;HiQH')z Di(epoxypr opoxypheny1)ethylphenylmethane- 2, 506, 486 O@H1CCH )(C H OH)1. Di(epoxypropoxyphenyl)propylphenylmethan 2, 506, 486 C HnC C|H )(O H OH); Dflepoxypropoxyphenyl)butylphenylmethane 2, 506, 486 (CH CQH Di(epoxypropoxypheny1)tolylmethane 2, 506, 486 (CH3C6H4)C Di(epoxypropoxy'phenyl)tolylmethylmethane 2,506,486 Dihydroxy diphenyl 4,4-bis(2,3epoxypropoxy)diphenyl 2, 530, 353 (OHE)C(C4H5.C5H3OH)2 2,2-bis(4-(2,3-epoxypropoxy)2-tertiarybutyl phenyDpropane-.- 2,530,353

V Subdivision B I V a 7 As to the preparation of low-molal polymeric epoxides In light of aforementioned U. S. Patent No. 2,575,558, or mixtures reference is made to numerous patents and 0 the following examples ean be specified by reference to particularly the aforementioned U. S. Patents Nos. 2,575,- th formulfllherem provided One still bears in mind it 558 and 2,582,985. is in essence an over-simplification.

' v TABLE II I w CC-C 0R [R],.R 0O-0-C OR1 [R]1| Ri0 C CC H: H H: H I H2 H: H H! (in which the characters have their previous significance) Example -R1O-irom HR OE 1 -R- 'n 1; Remarks number 1 B1 Hydroxy benzene CH3 .1 0,1,2 Phenol known as bis-phenol A.. Low polymeric mixture about $6 or more I where n=0, remainder largely where n=1, some where 'n=2. V I ,7 7 CH2 132.--; do CH; 1 0, 1,2 Phenol known as bis-phenol B. smote (I: regarding B1 above. I ([311: CH3 B3 Orthobutylphenol CH; 1 0,1, 2 Even though it is preferably 0, yet the i I usual reaction product might wellcon- O tain materials where n is 1, or to a I lesser degree 2. CH:

34....... Orthoamylphenol (EH; 1 0,1,2 Do.

B5 Orthooctylphenol (3H, 1 0,1,2 Do.

I CH:

136 orthononylphenol M (111; 1 '1 6,1,2 7' Do. 1 *f i (l} 5 I B7 Orthododeeylphenol 211, 1 0, 1,2 Do. E 1 (|7 M V 7 CH:

B'8 Metecresol CH 1 0,1,2 See prior note..-I1"his phenol used as r initial material is known as bis-phenol C C. For other suitable bis-phenols see U. S. Patent 2,564,191. q 7

CHI (EH, 7 1 0, 1,2 See prior note. V V

CH: V v 43H: "lji gbutyuprthd-p'ere)phenol, gr i 7 5,1,2 6 D0 7 7 H v 1 piamyl mud-pers mmon V p H 15 1 0,1,2 Do,

7 .11.. J51 H H As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and TABLE 11 (continued) Example R O from HR OH -R n n Remarks number B12 Dioctyl (ortho-para) phenoL 1(5)! 1 0, 1, 2 See prior note.

B13 Dinonyl (ortho-para) phenol- 13 1 0,1,2 D0.

B14 Diamyl (ortho-para) phenol. g 1 0,1,2 Do.

B15 do H 1 o, 1, 2 Do.

I CzHfi 1316.--..- Hydroxy benzene (i 1 0, 1, 2 D0.

B17 Diamyl phenoltortho-para). SS 1 0,1,2 Do.

B18 do H -S- 1 0,1, 2 D0.

B19 Dibutyl phenol (ortho-para)- 101 1g 1 0,1,2 Do.

1320 do. H H 1 0,1,2 D,o.

C .O. H H

B21 Dinonylphenol(ortho-para) g. 13 1 0,1,2 Do.

B22... Hydroxy benzene Y O 1 0,1,2 Do.

B23 dn Nn 0 0, 1,2 Do.

B24 Ortho-isopropyl phenol CH; 1 0,1,2 See prior note. As to preparation 0! 4,4- l isepropylidene bis-(2-isopropylphonel) -C see U. S. Patent No. 2,482,748, dated 1 Sept. 27, 1949, to Dietzler. CHa

1325...... Para-octyl phenol CHSCH1 1 0, l, 2 See prior note. (As to preparation of the phenol sulfide see U. 8. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeska et a1.)

1326...... Hydroxybenzene CH 1 0,1, 2 See prior note. (As to preparation oi the I phenol sulfide see U. S. Patent No. -c- 2,526,545.) 7

in I CgHs Subdivision C 60 may be illustrated by a phenol of the following composi The prior examples have been limited largely to those I p I i in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ke- 5 tone. Needless to say, the sameprocedure. is employed 65 E0 1 in converting diphenyl into a diglycidyl ether regardless l of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant. 7 0

Similar phenols which are monofunctional, for instance,

paraphe'nyl 'p'henol or'parac'yclohexyl phenol with an ad;

V isja substituent sielected fromthe class consisting of 2;7 7 1,438 15 16 with formaldehyde or sulfur chlorides to give comparable alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See phenolic compounds having 2 hydroxyls and suitable for U. S. Patent No. 2,5 subsequent reaction with epichlorohydrin, etc.

Other'samples include: 0H=0H OH OH 0 J) R 4 R1 OH 0: H OH 1's s 1 r J.

1'1 CH; JHI V w wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and a a R is a substituent selected from the class consisting of J i al y y oa y a y a y and alkaryl p nd See U. 5. Patent No. 2,515,908.

wherein said alkyl group contains at least 3 carbon atoms. As to sulfides, the following compound i of interest: See U. S. Patent No. 2,515,907. 05H 65Hv m csrmsp 0(osm0nn Q 6 Ct uUC r a u V 7 OH 01 As to descriptions of various suitable phenol sulfides,

, a s 7 reference is made to the following patents: U. S. Patents m which the --C5H11 groups are secondary amyl groups. I 4 321, 2,207,719, 2,174,248, 2,139,766, See U. S- Patent NO. 2,504,064. 2 4 0 1 and 2 195 539 '30, As to sulfones, see U. S. Patent No. 2,122,958...

See U. S. Patent No. 2,331,448. r I

& As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly com- HO OH pounds such as e e V See U. S. Patent No. 2,285,563. 5 7 13 H 13 H on; n on; A 5 our-(L0H. \(ll/ 4 'Alkyl R Alkyl OH: I g i in which R5 is a methylene radical, or a substituted methylj ene radical which represents the residue of an aldehyde l H and is preferably the unsubstituted methylene radicalderived from formaldehyde. See U. S. Patent No. 2,430,002. 011-011. See also U. s; Patent No. 2,581,919 which describes di- Q, (dialkyl cresol.) sulfides which include the monosulfides, g the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention: See U. S. Patent No. 2,503,196. W e

' OH OH; OH; OH

' OH: G S

($13: R, R1 R1 R I R in which R1 and R2 are alkyl groups, the, sum of whose carbon atoms equals 6 to about 20, and R1 and R2 each whereinrRt isf'aimemberiof'the group consisting of alkyl, Preferably Contain 3 t9 ab0J ..i19'a atoms, and X is and alkoxy-alkyl radicals containing from 1 to 5 carbon 1 h term l f f as 115651111 r sl 'q s atoms, inclusive, and aryl and chloraryl radicals of the inc ud s mqn ul de, .dlsulfide, and PQ Y j benzene series. See U. S. Patent No. 2,526,545.

l s 1 "f R Q A V s OH OH fIt is well 'known thatone can readily purchase on the open market, or prepare, fusible, organic solvent-soluble,

I R1 I water-insoluble resin polymers of acomposition approxi- R; mated in an idealized form by the formulav V I L w s 7'" V V 7 4 031 H; JOH I' QH 0 R1 is a substituent selected from the class cons 1sting of secondary butyl, and tertiary butyl groups. and

In the above formula n represents a small whole number varying from 1 to 6, 7, or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A

limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from .1 to 4; Rrepresents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl, or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patout No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. 8. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, lowstage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol and are formed in the substantial absence of trifunctional phenols. formula The 'phenol is of the in which R is an aliphatic hydrocarbon radical having at The basic hydroxylated amine may be designated thus:

RI HN particular aldehyde employed to form the resin.

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one-mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight exent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or buty'raldehyde. The resin unit may be exemplified thus:

in which R is the divalent radical obtained from the For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presense of a small amount of a free base. The amount maybe as small as a 200th of a percent and as much as a few 10ths of'a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However,

the most desirable procedure in practically every case is to I have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the'actual manufacture of the resins we found no reasonfor using other than those which are lowest'in priceand most readily available commercially. For pur- As has been pointed out previously, as far as the resin 7 It is usually a mixture; for

poses of convenience suitable resins are characterized in the following table:

TABLE III M01. wt. Exm of resin ample R Position derived 1:, molecule number of R from- (based on n+2) Phenyl Para Formal- 3 992. 5

dehyde Tertiary butyl.- do do 3 882. 5 Secondary butyl. Ortho... do 3 882. 5 Cyclohexyl. Para. do 3 1, 025. 5 Tertiary amyl do..." do 3 959.5 Mixed secondary Ortho... do... 3 805.6

and tertiary amyl. Propyl Parado 3. Tertiary hexyl. d 3. .1, ctyl 3. 1, Nonyl... 3. 1, Decyl.-- 3. 1, Dodecyl. 3. 1, Tertiary buty 3.

Tertiary amyl. Nonyl Tertiary butyl Tertiary amyl Nonyl Tertiary butyl. d

aldehyde.

Tertiary amyl Nonyl Tertiary butyl Tertiary amyl. Nonyl as -near. 2S

Hexy Gyclohexyl PART 5 As has been pointed out, the amine herein employed I valentfor divalent are alkyl, alkycyclic, arylalkyl, or hot;

erocyclic incharacter, subject of course to the inclusion of a hydroxyl group attached to a carbon atom which I amines there may be a s many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal prima'ry amino group or groups into a secondaryor tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal groupcould -be convertedinto a tertiary group and the other into a secondary amine, group. In the same way, I the polyamines can be subjected to hydroxyalkylation by reaction with ethylene oxide, propylene oxide, 'glycide, etc. In someinstances, depending on the structure, both types of reaction .may be employed, i. e., one type'toi introduce a hydroxy ethyl group, for example, and an-- other type to introduce a methyl or ethyl radical.

By way of example the following formulas are included. It will be noted they include such polya'mines:

, which, instead of being obtained from ethylenedichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a. carbon atom chain interrupted by an oxygen atom:

. H NpropyleneNp -opyleneN QgHlOH HOCQHA N C zHiN CaHiN CzH4N I HOCzH4 Another procedure for producing suitable 'polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkyl- 1 one oxide, such as ethylene oxide, propylene oxide or glycide.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzyl- -amine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylene oxide followed by reaction with an imine-and then the use of an alkylene, oxide Similarly, one can start with a primary amine and introduce two moles of an alkylene oxide so as to again.

have a compound comparable to ethyl diethanolamine and react with two moles of an imine and then with two I moles of ethylene oxide.

Reactions involving the same reactants previously described, i. e., a suitable secondary monoamine plus an alkylene imine plus an alkylene oxide, or a suitable mono-E amine plus an alkylene oxide plus an alkylene imine and plus the second introductionof an alkylene oxide, can ,be applied to a variety of primary amines. In the case of primaryamines one can eithenemploy'twq moles of an-alkylene oxide so as to convert both amino hydrogen atoms into an alkanol group, or the equivalent; or else the primary amine can be converted into a secondary amine by the alkylation reaction. In any event, one'can obtain a series of primary amines'andco'rresponding secondary amines which are characterized by the fact that such amines include groups having repetitious ether linkages and thus introduce a definite hydrophile effect 5. JW virtue of the ether linkage. Suitable polyether amines amines Susceptible to Conversion in the manner describedinclude those of the formula in which x is a small whole number having a value of l or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to 1, with the proviso that the sum of m plus in equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to Wit, U. S. Nos. 2,325,514, dated July 27, 1943 to Hester, and 2,355,337 date'd'August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as CH3OC2H4CI Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so ob-' tained and suitable for conversion into appropriatepolyamines are exemplified by (CI-IsOCHz CHzCHzCI-IzCHzCHz zNH Other similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition R0(0Hi)a\ /NH R-O (CHzh as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula K may be methyl, ethyl, prooyl, amyl, octyl, etc.

Other suit-able secondary amines which can beconverted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine' or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No.

2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following; beta phenoxyethylamine, gamma phenoxypropylamine, beta-phenoXy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517, and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as with the statement that such presentation is an over-simplification. It was pointed out that at least one occurrence of R must include a secondary amino radical of the kind specified. Actually, if the polyamine radical Icon-.

tains two or more secondary amino groups theamine may be reactive at two different positions and thus the, same amine may yield compounds in which R and R are dissimilar.

H /NpropyleneNpropy1eneN H N C2H4NCzH NC :H4NC2H4N H H H HOCZH4 C2H4OH In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than-if the reaction took place at the intermediate secondaryamino radical as differentiated from the terminal group. Again, referring to the second formula above, although a' terminal amino radical is not involved it is obvious again that one could obtain two difierent structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending on whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by.

the :above "examples it 'is obvious that one might get a} mixture in which in part'the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of Icompoundsmight be obtained due to such multiplicity of reactive radicals. This can be illustrated,

by the following formula:

OH:\ CH: NCzHtN CaH'4NCnH4NC2H4N n H H H Cz'HtOH Certain hydroxylated polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction maybe illustrated by the following additional examples:

i As-is well known one can prepare ether amino alcohols of the type KOCH2CH(OH) CH2NHCH2 g CH2NHCI'I2CH(OH)CH2OR in which R represents an alkyl group varying from methyl to'normal decyl, and in fact, the group may contain as many as or even carbon atoms. See J. Org. Chem., 17,2 (1952). f y a Over 'andabove the specific examples which have appeared previously, attention is directed to the fact that a number of suitable amines are included in subsequent Table IV.

PART 6 The products obtained by the herein described processes represent cogeneric mixtures'which are the result of a condensation reaction or reactions. .Since the resin molecule cannot be defined satisfactorily by formula, al-

though it may be so illustrated inan idealized simplification, it is diflicult to actually depict the finalproduct of the cogeneric mixture except in terms of the process itself.

Previous reference has been made tothe fact that the procedure herein employed is comparable, in a general Way, to that which corresponds to somewhat similar derivatives made either from phenols as'differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly'selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned-U. S. Patent No. 2,499,368.

I In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequenlty described; in fact,

' usually it is apt to be a solid at distinctly higher temperaare not here included as raw materials. The reaction can he conducted inrsucha way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether-of ethyleneglycol. Onecanalso use a mixture of benzene orxylene and such oxygenated solvents. Note that the use of such oxygenatedsolvent is not required'in the sense that it is not necessary to use an initial resin which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason thatin most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be dilluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In

any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxalkylation, then, obviously, the alcohol should not be used or else it should beremoved. The fact that an oxygenated solvent neednot be employed, of course, is an advantage for reasons stated. I j

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some or the initial solvent is apt to remain without complete removal; Even if one starts with a resin which is almost invariably a dark red in :color or at least a red-amber, or some colorwhich includes both an amber component and a reddish component. 'By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on theresin selected and on the amine selected the condensationproduct I or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

:The products obtained, depending on the reactants selected', may be water-insoluble or water-dispersible, or water-soluble, or" close to being water-soluble. Water solubility is enhanced, of :course, by making a solution in the acidified vehicle such as a dilute solution, for instance,

a 5% solution of hydrochloric acid, acetic acid, hydroxy-' acetic acid, etc. One also may convert the finished product into'salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next suceeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using atemperature of not over C. and employing vacuum,

' 1 if required. This applies, of course, only to those circumstances where 'itis desirable or necessary to remove the solvent. be used. The selection of solvent, such as benzene, xylene, or the like, depends'primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to'furtherreaction in which the solvent, for instance, an alcohol, either low boiling or high ,boiling, might inter:

Petroleum solvents, aromatic solvents, etc., can

fere as in the case of oxyalkylation? and the third factor is this, is an effort to be made to purify the reaction mass by the usual procedure as, for example, a waterwash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are Well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent. I

We have found no particular advantage in using a low temperature in the early stages of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bcarsome similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easierto prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacuring there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. formaldehyde loss or make it easier to control unreacted formaldehyde loss. 1

On a large scale if there is any difliculty with formalde- 30% formaldehyde may tend to decrease any hyde loss control, one can use a more dilute'form'of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to l024 hours, We then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction. and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have. not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously little more need be said as to the actual procedure employed for.

the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding, were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl)ethylenediamine were added. The mixture was stirred vigorously and formaldehyde used was a 30% solution and the amount employed was 200 grams. It was added in a little over 3 hours. The mixture was stirred vigorously and kept within a temperature range of 33 to 48 C. for about 17 hours. At the end of this time it was refluxed using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within about 3 hours or thereabouts. As soon as the odor of formaldelIYd'E, was no longer particularly noticeable or detectible the phase-separating trap was set so as to eliminate part 'of the xylene was removed until the temperature reached approximately 150 C. or perhaps a little higher. The reaction mass was kept at this temperature for a little over 4 hours and the reaction stopped. During this time any additional water, which was probably water of reaction whichhad formed, was eliminated'by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample Was heated on a water bath to remove the excess Xylene. The residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat under 30 hours. In other examples it varied from 24 to more than 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table IV following there are a large number of added examples illustrating the. same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phaseseparating trap was employed to separate out all the water, both the solution and condensation; After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is Amine B- CrHa Oa eO NGzHtN Amine 0- HO CzH4 Oz 4OH /NO:HuN\ H H Amine D- CH2CH2 CHr-GHI HOCH HCNH-CHaCH2-NHCH HCOH out-om CHrCH:

(3H5 H 2 4 )2 Amine E H-CNCH2-CCH3 CH CH2 Amine F H0 omorrmrr-o'm HOCHzCHzNH-CH HO CH2CHzNH-CHr Amine H- CHaNHCHz CHaNHCHr-CHZOH CHsNHCH:

Amine I PART 7 illustrated by 24 examples in Table IV. 45 ates. Subsequent oxyalkylation involves the use of ethyl- TABLE IV Strength of Reac- Reae- Max. Ex. Resin Amt, Amine used and amount formalde- Solvent used tion tion distill N 0. used grs. hyde soln. and amt. temp time, temp.,

and amt. 0. hrs. C.

882 Amine A, 296 g 30%, 200 g... Xylene, 500 g--. 21-24 24 150 480 Amine A, 148 g. 37%, 81 g Xylene, 480 g 20:23 27 156 633 do do 25 142 441 Amine B, 176 28 480 do 34 633 do 30 152 882 Amine O, 324 88 141 480 Amine C, 162 g 20 21 25 e 143 633 do 23 24 25' 140' 473 Amine D, 256 g 22 25 25' 148 511 do 20 21 25. 158 665 do Xylene, 525 g 21-25 28 152 441 Amine E, 208 g. Xylene, 400 22-24 g 26 i 143; 480 do do 25-27 v 36. 144 595 do Xylene, 500 g. 26-27. 34 141 441 Amine F, 236 g. Xylene, 400 g. 21-23 25 153 i 480 do do 20-22 28 150 511 ....do 'Xylene, 500 g 23-25 27 155 498 Amine G, 172 g. Xylene, 400 g. 34 150 542 d0 c Xylene, 450 g. 36 1 52 547 Amine H, 221 30 148 441 .do '24 143 595 Amine I, 172 g V Xylene, 450 g. V 32 H 15l 391 Amine I, 86 g Xylene, 300 g.. 20-26 86 147 As to the formulas of the above amines referred to as Amine A through Amine I, inclusive, see immediately following: l p V Amine A- HO 01H 0.114011 ene oxide, propylene oxide, butylene oxide, glycide, etc. Such oxyalkylating agents are monoepoxides as dif fere'ntiatedfrom polyepoxides. V p I i It becomes apparent that if the product obtained is to be treated subsequently with a monoepoxide which may re Y 75 quire a pressurevessel as in thecase of'ethyleneoxide, it

is convenient to use the same reaction vessel in both instances. In other words, the 2 moles of the amine-modified phenol-aldehyde resin condensate would be reacted with a polyepoxide and then subsequently with -a monoepoxide. In any event, if desired the polyepoxide reaction can be conducted in an ordinary reaction vessel, such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, U. S. Patent No. 2,499,365.

Cognizance should be taken of one particular feature in connection with the reaction involving the polyepoxide and that is this; the amine-modified phenol-aldehyde resin condensate is invariably basic and thus one need not add the usual catalysts which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usual catalyst includes alkaline materials such as caustic soda, caustic potash sodium methylate, etc. Other catalyst may be acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalyst have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactant, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes Without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylation-susceptible. Generally speaking, this is more conveniently an aromatic solvent such as xylene or ahigher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or an aromatic petroleum will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

densate 2b. Condensate 2b was obtained from resin 5a. Resin 6a was obtained from tertiary amylphenol and gradually rose to 170 C. or slightly less.

formaldehyde. The amount of resin employed was 480 grams. The amount of amine employed (Amine A) was 148 grams. The amount of 37% formaldehyde employed was 81 grams. The amount of solvent employed was 480 grams. Amine A, as previously indicated at the end of Table IV, preceding, was symmetrical di(hydroxyethyl)'- ethylene diamine. All this has been described previously.

The solution of the condensate in xylene was adjusted to a 50% concentration. In this particular instance, and in practically all the others which appear in the subsequent table, the examples are characterized by the fact that no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, a small amount of alkaline catalyst could be added, such as finely powdered caustic soda, sodium methyl-ate, etc. If such alkaline catalyst is added it may speed up the reaction but it also may cause an undesirable reaction, such as the polymerization of the diepoxide.

In any event, 128 grams of the condensate were dissolved in approximately an equal weight of xylene and stirred and heated to C. 17 grams 10f the diepoxide previously identified as 3A, and dissolved in an equal weight of xylene, were added dropwise. The initial addition of the xylene solution carried the temperature above 109 C. The remainder of the diepoxide was added in about an hours time. During this period of time the temperature rose somewhere above C. The prodnot was allowed to reflux at about C., using a phaseseparating trap. A small amount of xylene was removed by means of the phase'separating trap as the temperature The mixture was then refluxed at about this same temperature for about 4 or 5 hours until the reaction had stopped and the xylene which had been separated out during the reflux period, was returned to the mixture. The. overall reaction time was about 7 hours. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to examine the physical properties. The material was a dark red viscous semi-solid. It was insoluble in water, it was insoluble in a 5% gluconic acid solution, and it was soluble in xylene, and particularly in a mixture of 80 parts xylene and 20 parts methano-l. However, if the material was dissolvedin an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

The procedure employed of course is simple in light of what has been said previously and in effect is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylating agents. See, for Example Part 1 of U. S. Patent No. 2,602,062 dated July 1, 1952, to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

TABLE V Gon- Time Ex den- Amt, Diep- Amt, Xylen Molar of reac- Max No sate grs. oxide grs. grs. ratio tion, temp Color and physical state used used hrs. 0

128 3A 17 2:1 7 170 Dark semi-solid. 134 3A 17 2:1 8 168 D0. 123 3A 17 140 2:1 7 175 D0. 130 3A 17 147 2:1 7 172 Do. 148 3A 17 2:1 8 168 Do. 187 3A 17 204 2:1 8 175 Dark solid mass. 132 3A 17 150 2:1 8 16 Do. 152 3A 17 2:1 8 170 D0. 136 3A 17 153 2:1 8 165 D0. 145 3A 17 162 2:1 8 170 Do.

TABLE V1.

Con- Time Ex. den- Amt, Diep- Amt, Xylene, Molar of reac- Max No. sate grs. oxide grs. grs. ratio tion, temp., Color and physical state used used hrs. 0.

128 B1 27. 156 2:1 7 165 Dark semi-solid. 134 B1 27.5 162 2:1 7 170 Do. 123 B1 27. 5 150 2:1 7 170 Do. 130 B1 27. 5 158 2:1 7 175 D0. 148 B1 27. 5 176 2:1 8 172 Do. 187 B1 27. 5 215 2:1 8 168 Dark solid mass. 132 B1 27. 5 160 2:1 7 170 Do. 152 B1 27. 5 180 2:1 8 175 D0. 136 B1 27. 5 164 2:1 8 165 D0. 145 B1 27. 5 173 2: 1 8 180 D0.

Solubility in regard to all these compounds was substantially simllarto that which was described in Example 10.

TABLE VII Probable Resin con- Probable Amt. of. Amt. of number of Ex. No. densate mol. wt. of product, solvent, hydrowls used reaction grs. grs. per moleproduct cule TABLE VIII Probable I Resin con- Probable Amt. 0t Amt. of number of Ex. No. densate mol. wt. of product, solvent, hydroxyls used reaction grs. grs. per moleproduct cule At this point it may be desirable to direct attention to two facts, the first being thatwe are aware that other diepoxides free from anaromatic radical as, for example, 'epoxides derived from ethylene glycol, glycerine, or the like, such as the following:

may be employed to replace the diepoxides herein described. However, such derivatives are not included as part of the instant invention.

At times we have found a tendency for an insoluble mass to form or at least to obtain-incipient cross-linking or gelling even when the mo-lal ratio is in order of 2 moles of resin to .one -'of diepoxide. this can be avoided by', any one of the following procedures or their equivalent. Dilute-the resin' or the diepoxide, or both, with an inert solvent, such as xylene or the like. such as the diethyl' ether of ethyleneglyool may be employed. Another procedure which is helpful is to re-f duce the amount of catalyst used, or reduce the tempera-' We have found In some instances an oxygenated solvent,f

ture of reaction by adding a small amount of initially" of diepoxide, for instance, to instead of The reason for this fact may reside in the possibility I that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensate has. been depicted in a simplificd form which, for convenience, may be shown thus:

in which D. G. E. represents a diglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as 7 indicated by the following f ormulas:

[(Amine) CHz(Amine)] /D.G.E. [(Amine) criminals Resin) CHr(Resin)] V /D.G.E. [(Resin) GH (Resin)] [(Amlne)CHz(Amine)l V 7 D.G.E.,

, e ml I V V All the above indicates the complexity of .the reaction product obtained after treating the amine-modified resin condensate with apolyepoxide and particularly diepoxide as herein described.-

I PART 8 1 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, parhexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitablejf well-known classes of demulsifying agents. f

It is well known that conventional demulsifying agents may be used in a water-solubleform, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

In practicing the present process, the treating or demulsifying agent is used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part Three, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and doWn-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mix ture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

The demulsifier of the present invention, for example, the product of Example 1C, 20%

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described our invention, what We claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxylation-susceptible, fusible, nonoxygenated organic solvent-soluble water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting said resin condensate with a phenolic polyepoxide free from reactive functional groups other than epoxy and hydroxyl groups and cogenerically associated compolmds formed in the 34 preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramers; said polyepoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehyde oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical CH2SCH2-, and the divalent disulfide radical -SS; said phenolic portion of the diepoxides being obtained from a phenol of the structure in which R, R", and K represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be: a member of the class of solvent soluble liquids and low-melting solids; said reaction between (A) and (B) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the phenolic polyepoxide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substiuted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine' radical; and (0) formaldehyde; said condensation reaction being conducted'at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction;

and with the proviso that the resinous condensation prod- I not resulting from the process be heat-stable and oxyalkyladon-susceptible; followed by (B) reacting phenolicepoxides being principally polyepoxides,.;.includin g phenolic diep oxides; said epoxides being free from reactive functional groups other than epoxy andhydroxyl groups, and including additionally cogenerically associated compounds formed in the preparation of, said polyep'oxidesrand diepoxides, said epoxides. being monomers and low molal polymers not exceeding the tetramer; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the lzetonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent radical, and divalent sulfone radical, and the divalent radical --CHzSCI-Iz, and thevdivalent disulfide radical SS; said phenolic portion of the diepoxide bein obtained from a phenol of the structure in which R, R", and R" represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solventsoluble liquids and low-melting solids; and said reaction between (A) and (B) be conducted below the pyrolytic point of the reactants and resultants -of'reaction.

3. A process for breaking petroleum'emulsions of the water-in-oil type characterized by subjecting the emulsion 36 I aldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous con densation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than epoxytand hydroxyl groups, and cogenerically associated compounds formed in the preparation of said diepoxides; said epoXides being monomers and low molal polymers not exceeding the tetramers; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) com: pounds containing a radical in which 2 phenolic-nuclei are joined by a divalent radical selected from the class to the action of a demulsifier, said demulsifier being in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (c) formconsisting of ketone residues formed by the elimination of the ketonic oxygen atom, and, aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical r and the divalent disulfide radical said phenolic portion of the diepoxide being obtained from a phenol of the structure A!!! IR in which R, R, and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of solvent-soluble liquids and low-melting solids; and said reaction between (A) or (B) be conducted below the pyrolytic point of the reactants and the resultants of reaction,

4. A process for breaking water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained byfirst (A) condensing (a) anoxyalkylation susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight 'correspondingto at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at' least 4 and not more than 24 carbon atoms and-sub stituted in the 2,4,6 position; (b) a basichydroxylated.

petroleum emulsions of the 37 polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than epoxy and hydroxyl groups, and cogenerically associated compounds formed in the preparation of said diepoxides'; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom,

and aldehyde residues obtained, by the elimination of the I ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S-, the divalent radical CHzSCH2 and the divalent disulfide radical SS; said phenolic portion portion of the diepoxide being obtained from a phenol of the structure in which R, R", and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the ratio of reactant (A) to reactant (B) being at least suflicient so there is available at least one active hydrogen in (A) for each oxirane ring in the diepoxide reactant (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) be conducted below the pyrolytic point of the reactants and the resultants of reaction.

5. A process for breaking petroleumemulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the sub- 38 stantial absence of tri'ftmctionai phenols; said phenol being of the formula the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resultingfrom the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than epoxy and hydroxylgroups, and cogenerically associated compounds formed in the preparation of said diepoxides, including monoepoxides; said cogenerically associated compounds containing an average of more than one epoxide group per molecule; said epoxides being monomers and low molal polymers not exceeding the tetramers; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (lab) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent 0 II C radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical and the divalent disulfide radical -SS; said phenolic portion of the diepoxidebeing obtained from a phenol of the structure r in which R, R, and R' represent a member of the class consisting of hydrogen and hydrosubstituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the ratio of reactant (A) to reactant (B) being at least sufficient so there is available at least one active hydrogen in (A) for each oxir-ane ring in the diepoxide reactant (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and lowamelting solids; With the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the re sultants of reaction. a v i 6. A process for breaking petroleum emulsions of the water-in-oil type characterized by'subiecting the emulsion a said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R"" is an aliphatic hydrocarbon radical having at least 4 and .not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a'basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with'the proviso that the resi nous condensation product resulting from the process in which R represents a divalent radical selected from the class consisting of ketone residues formed by the elimination of'the ketonic oxygen atom and aldehyde residuesiobtained by the elimination of the aldehydic oxygen atom, the divalent radical H H C O H H the divalent c radical, the divalent sulfone radical, and the divalent monosulfide radical -S-, the divalent radical and the divalent disulfide radical SS and R10 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol l R!!! RI! I in which R, R", and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic-nucleus, said substituent member having not over 18 carbon atoms; the ratio of reactant (A) to reactant (B) being at least sufficient so there is available at least one active hydrogen in (A) for each '40 (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below thepyrolytic point of the reactants and the resultants of reaction.

7. A process for breaking petroleum emulsion of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier said demulsifier being obtained by first (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula t.

in which R"" is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hy'droxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and O Y 2 wherein R is an aliphatic hydrocarbon bridge, each 11 independently has one of the values 0 to 1, and R1 is an alkyl radical'containing froml to 12 carbon atoms, and

(bb) cogenerically associated compounds formed in the preparation of (aa) preceding, including monoepoxides with the proviso that (B) consist principally of the monomer as distinguished 'from other cogeners; the ratio of reactant (A) to' reactant (B) being at least suificient so there is available at least one active hydrogen in (A) for each oxirane ring in the diepoxide reactant (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

8. A process for breaking petroleum emulsions of the water-in-oil type" characterized by subjecting the emulsion to the action of a demulsifier said demulsifier being obtained by first (A) condensing (a) an oxyalkylation- 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER, SAID DEMULSIFIER BEING OBTAINED BY FIRST (A) CONDENSING (A) AN OXYLATION-SUSCEPTIBLE, FUSIBLE, NONOXYGENATED ORGANIC SOLVENT-SOLUBLE WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 